Textiles capable of capture and detoxification of toxic chemicals, such as chemical-warfare agents (CWAs), are of high interest. Some metal-organic frameworks (MOFs) exhibit superior reactivity toward CWAs. However, it remains a challenge to integrate powder MOFs into engineered materials like textiles, while retaining functionalities like crystallinity, adsorptivity, and reactivity. Here, we present a simple method of electrospinning UiO-66-NH, a zirconium MOF, with polyvinylidene fluoride (PVDF). The electrospun composite, which we refer to as "MOFabric", exhibits comparable crystal patterns, surface area, chlorine uptake, and simulant hydrolysis to powder UiO-66-NH. The MOFabric is also capable of breaking down GD (O-pinacolyl methylphosphonofluoridae) faster than powder UiO-66-NH Half-life of GD monitored by solid-state NMR for MOFabric is 131 min versus 315 min on powder UiO-66-NH.

TiO(2)-supported gold nanoparticles exhibit surprising catalytic activity for oxidation reactions compared to noble bulk gold which is inactive. The catalytic activity is localized at the perimeter of the Au nanoparticles where Au atoms are atomically adjacent to the TiO(2) support. At these dual-catalytic sites an oxygen molecule is efficiently activated through chemical bonding to both Au and Ti(4+) sites. A significant inhibition by a factor of 22 in the CO oxidation reaction rate is observed at 120 K when the Au is preoxidized, caused by the oxygen-induced positive charge produced on the perimeter Au atoms. Theoretical calculations indicate that induced positive charge occurs in the Au atoms which are adjacent to chemisorbed oxygen atoms, almost doubling the activation energy for CO oxidation at the dual-catalytic sites in agreement with experiments. This is an example of self-inhibition in catalysis by a reactant species.

A fullerene-based photosensitizer is incorporated postsynthetically into a Zr -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the overall generation of singlet oxygen from the material under UV irradiation. The singlet oxygen generated by the MOF/fullerene material is shown to oxidize sulfur mustard selectively to the less toxic bis(2-chloroethyl)sulfoxide with a half-life of only 11 min.

For the first time, an increasing number of defects were introduced to the metal-organic framework UiO-66-NH in an attempt to understand the structure-activity trade-offs associated with toxic chemical removal. It was found that an optimum exists with moderate defects for toxic chemicals that react with the linker, whereas those that require hydrolysis at the secondary building unit performed better when more defects were introduced. The insights obtained through this work highlight the ability to dial-in appropriate material formulations, even within the same parent metal-organic framework, allowing for trade-offs between reaction efficiency and mass transfer.

Zirconium hydroxide (Zr(OH)) has excellent sorption properties and wide-ranging reactivity toward numerous types of chemical warfare agents (CWAs) and toxic industrial chemicals. Under pristine laboratory conditions, the effectiveness of Zr(OH) has been attributed to a combination of diverse surface hydroxyl species and defects; however, atmospheric components (e.g., CO, HO, etc.) and trace contaminants can form adsorbates with potentially detrimental impact to the chemical reactivity of Zr(OH). Here, we report the hydrolysis of a CWA simulant, dimethyl methylphosphonate (DMMP) on Zr(OH) determined by gas chromatography-mass spectrometry and in situ attenuated total reflectance Fourier transform infrared spectroscopy under ambient conditions. DMMP dosing on Zr(OH) formed methyl methylphosphonate and methoxy degradation products on free bridging and terminal hydroxyl sites of Zr(OH) under all evaluated environmental conditions. CO dosing on Zr(OH) formed adsorbed (bi)carbonates and interfacial carbonate complexes with relative stability dependent on CO and HO partial pressures. High concentrations of CO reduced DMMP decomposition kinetics by occupying Zr(OH) active sites with carbonaceous adsorbates. Elevated humidity promoted hydrolysis of adsorbed DMMP on Zr(OH) to produce methanol and regenerated free hydroxyl species. Hydrolysis of DMMP by Zr(OH) occurred under all conditions evaluated, demonstrating promise for chemical decontamination under diverse, real-world conditions.